CN101810983A - Method for regenerating nitrogen oxide complexed absorption liquid in smoke denitration - Google Patents
Method for regenerating nitrogen oxide complexed absorption liquid in smoke denitration Download PDFInfo
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- CN101810983A CN101810983A CN201010123258A CN201010123258A CN101810983A CN 101810983 A CN101810983 A CN 101810983A CN 201010123258 A CN201010123258 A CN 201010123258A CN 201010123258 A CN201010123258 A CN 201010123258A CN 101810983 A CN101810983 A CN 101810983A
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- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 238000010521 absorption reaction Methods 0.000 title claims abstract description 38
- 238000000034 method Methods 0.000 title claims abstract description 24
- 239000007788 liquid Substances 0.000 title claims abstract description 22
- 230000001172 regenerating effect Effects 0.000 title claims abstract description 6
- 239000000779 smoke Substances 0.000 title description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000011259 mixed solution Substances 0.000 claims abstract description 27
- 241000894006 Bacteria Species 0.000 claims abstract description 24
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 23
- 238000006722 reduction reaction Methods 0.000 claims abstract description 22
- 239000002245 particle Substances 0.000 claims abstract description 13
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000003546 flue gas Substances 0.000 claims abstract description 12
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 10
- 239000004020 conductor Substances 0.000 claims abstract description 6
- 239000002184 metal Substances 0.000 claims abstract description 4
- 229910052751 metal Inorganic materials 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 44
- 239000007640 basal medium Substances 0.000 claims description 23
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 15
- 239000008103 glucose Substances 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 230000008569 process Effects 0.000 claims description 10
- 239000010439 graphite Substances 0.000 claims description 8
- 229910002804 graphite Inorganic materials 0.000 claims description 8
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 6
- 239000004917 carbon fiber Substances 0.000 claims description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 6
- WFJIVOKAWHGMBH-UHFFFAOYSA-N 4-hexylbenzene-1,3-diol Chemical compound CCCCCCC1=CC=C(O)C=C1O WFJIVOKAWHGMBH-UHFFFAOYSA-N 0.000 claims description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 5
- RHZUVFJBSILHOK-UHFFFAOYSA-N anthracen-1-ylmethanolate Chemical compound C1=CC=C2C=C3C(C[O-])=CC=CC3=CC2=C1 RHZUVFJBSILHOK-UHFFFAOYSA-N 0.000 claims description 5
- 239000003830 anthracite Substances 0.000 claims description 5
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 230000005611 electricity Effects 0.000 claims description 4
- 239000008187 granular material Substances 0.000 claims description 4
- 229910021397 glassy carbon Inorganic materials 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- VFNGKCDDZUSWLR-UHFFFAOYSA-L disulfate(2-) Chemical compound [O-]S(=O)(=O)OS([O-])(=O)=O VFNGKCDDZUSWLR-UHFFFAOYSA-L 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 claims description 2
- 238000009418 renovation Methods 0.000 claims 7
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 abstract description 63
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 abstract description 32
- 230000009467 reduction Effects 0.000 abstract description 9
- 230000008929 regeneration Effects 0.000 abstract description 5
- 238000011069 regeneration method Methods 0.000 abstract description 5
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 abstract description 2
- 230000001580 bacterial effect Effects 0.000 abstract 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 63
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical compound [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 18
- 229910052760 oxygen Inorganic materials 0.000 description 12
- 239000000047 product Substances 0.000 description 12
- 244000005700 microbiome Species 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 235000015097 nutrients Nutrition 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 6
- 230000001603 reducing effect Effects 0.000 description 6
- 239000002131 composite material Substances 0.000 description 5
- 239000012141 concentrate Substances 0.000 description 5
- 239000000470 constituent Substances 0.000 description 5
- 229910052742 iron Inorganic materials 0.000 description 5
- 230000000813 microbial effect Effects 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 238000011081 inoculation Methods 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000000536 complexating effect Effects 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 230000002829 reductive effect Effects 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 230000001651 autotrophic effect Effects 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 238000005842 biochemical reaction Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000012737 fresh medium Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000001963 growth medium Substances 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 2
- 229910000859 α-Fe Inorganic materials 0.000 description 2
- FRXSZNDVFUDTIR-UHFFFAOYSA-N 6-methoxy-1,2,3,4-tetrahydroquinoline Chemical compound N1CCCC2=CC(OC)=CC=C21 FRXSZNDVFUDTIR-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 230000010757 Reduction Activity Effects 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000001493 electron microscopy Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 244000000010 microbial pathogen Species 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 230000005619 thermoelectricity Effects 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
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- Water Treatment By Electricity Or Magnetism (AREA)
Abstract
本发明公开了一种用于烟气脱硝中再生氮氧化物络合吸收液的方法，(1)以碳质材料为阳极，金属导体或碳质材料为阴极，在阴极周围填充导电粒子制成三维电极；(2)将三维电级进行混合菌的挂膜，制得附有混合菌膜的三维电级；所述的混合菌为反硝化菌和铁还原菌的混合培养物；(3)外加电子供体、碳源和基础培养基于氮氧化物络合吸收产物中制得混合溶液，然后将附有混合菌膜的三维电极置入混合溶液中并通电，进行还原反应。本发明提供的方法适用于络合吸收-生物还原系统中络合吸收液的再生，大大提高了Fe(II)EDTA-NO和Fe(III)EDTA的还原速率，操作简单，经济成本低，占地小，二次污染小。The invention discloses a method for regenerating nitrogen oxide complex absorption liquid in flue gas denitrification. (1) a carbonaceous material is used as an anode, a metal conductor or a carbonaceous material is used as a cathode, and conductive particles are filled around the cathode Three-dimensional electrode; (2) The three-dimensional electrode is subjected to the hanging film of mixed bacteria to obtain a three-dimensional electrode with mixed bacterial film; the mixed bacteria is a mixed culture of denitrifying bacteria and iron-reducing bacteria; (3) Add electron donor, carbon source and basic culture to prepare mixed solution based on nitrogen oxide complex absorption product, then put the three-dimensional electrode with mixed bacterial film into the mixed solution and electrify to carry out reduction reaction. The method provided by the invention is applicable to the regeneration of the complex absorption liquid in the complex absorption-biological reduction system, greatly improves the reduction rate of Fe(II)EDTA-NO and Fe(III)EDTA, is simple to operate, low in economic cost, and accounts for The land is small and the secondary pollution is small.
Description
Technical field
The present invention relates to the environmental pollution improvement field, refer to a kind of method that is used for the denitrating flue gas regenerating nitrogen oxide complexed absorption liquid particularly.
Background technology
NO
xIt is the one of the main reasons that causes a series of serious air pollution problems inherent such as acid rain, photochemical fog.At present, China's thermoelectricity industry nitrogen oxide emission is huge, presses for control." the discharged nitrous oxides control technology project study report of Chinese thermal power plant " of Chinese environmental protection industry association tissue shows, the nitrogen oxide total amount of power plants discharging in 2007 has increased to 8,400,000 tons, increased closely 40.6% than 597.3 ten thousand tons in 2003, accounted for 35%～40% of national nitrogen oxide emission.Because smoke discharge amount is big, and NO in the flue gas
xThe solubility of main component nitric oxide (accounting for 95%) in water very low, intractability is bigger.So far, NH only in the world
3SCR (SCR) and SNCR (SNCR) industrial applications that obtained certain scale.But existing these two kinds of technology still exist the financial cost height, produce defectives such as secondary pollution or treatment effeciency are low (Radojevic M, " Environ.Pollut. ", 1998,102,685-689).Thereby, develop new gas denitrifying technology and become one of research focus of field of environment protection.
The Japan and the U.S. just add ferrous chelating agent since the seventies in 20th century and carry out the while desulfurization removing nitric in the cleaning solution of flue gas desulphurization system.Add nitrogen oxide complexed absorption liquid (Fe (II) EDTA) complexed absorption NO and generate Fe (II) EDTA-NO, can significantly improve the mass transfer rate of NO from the gas phase to the liquid phase.And problem is that Fe (II) EDTA is easy to be oxidized to Fe (III) EDTA that does not have complexing NO ability, and the agent of Fe (II) EDTA complexed absorption is difficult to regeneration and recycling.Utilize the nitrogen oxide complexed absorption product of micro-reduction (mixed system that mainly constitutes) by Fe (II) EDTA-NO, Fe (III) EDTA, can solve the regeneration problem of absorbent well, so complexed absorption-biological reducing denitrating flue gas arises at the historic moment.But (Li W, " Chem.Techno.Biotechnol. ", 2006,81,306～311 are found in correlative study; Li W, " Environ.Sci.Techno. ", 2007,41,639-644), the reduction efficiency of Fe (II) EDTA-NO and Fe (III) EDTA is the key of system's continous-stable running, and how to improve microbial activity, and strengthen rate of reduction, become the task of top priority of this technical development.
Since the nineties, the electrode biomembrane method is used for the waste water denitrification denitrogenation and has obtained very big development.Under electro-catalysis, the microorganism of cathode surface can utilize organic matter and additional power source to produce hydrogen as electron donor simultaneously, and the reducing activity of microorganism is improved, thereby denitrification denitrogenation efficient is strengthened (Xu Baixing, " pollution prevention technique ", 1998,11,1,45-47).Chinese scholars has been carried out big quantity research to this technology, wherein by improving electrode structure, more makes current efficiency and denitrification efficient have significantly and promotes.2002, employing active carbon particle layers such as Prosnansky were made cathode material, had increased cathodic surface area greatly, and make being adsorbed on the particle surface that microorganism can be firm fast, quicken formation (Prosnansky M, " Wat.Res. " of film, 2002,36 (1), 4801-481).The denitrogenation speed of this reactor is 3-60 times before improving, and has realized the short time efficient denitrification.There are some researches show that in addition it all is by utilizing H that most alienation Fe (III) go back pathogenic microorganism
2(He Jiangzhou, microbiology circular, 2006,33 (5), 158～164) of growing with organic electronic donor reduction Fe (III).
Summary of the invention
The invention provides the method for reducing of the nitrogen oxide complexed absorption product that a kind of energy consumption is little, efficient is high, cost is low, to solve the problem of the reducing activity of microorganism in complexed absorption-biological reducing system.
A kind of method that is used for the denitrating flue gas regenerating nitrogen oxide complexed absorption liquid may further comprise the steps:
(1) with the carbonaceous material be anode, metallic conductor or carbonaceous material are negative electrode, fill the clastic conducting particles and make three-diemsnional electrode around negative electrode;
(2), make with three-dimensional electric grade that mixes mycoderm with three-dimensional electric grade of biofilm of carrying out Mixed Microbes;
Described Mixed Microbes is the mixed culture of denitrifying bacterium and iron-reducing bacterium;
(3) add electron donor, carbon source and basal medium and in nitrogen oxide complexed absorption product, make mixed solution, will insert in the mixed solution and energising with the three-diemsnional electrode that mixes mycoderm then, carry out reduction reaction.
Described nitrogen oxide complexed absorption product is that nitrogen oxide complexed absorption liquid (Fe (II) EDTA solution) absorbs the mixed system that NO forms in the flue gas, wherein mainly comprises Fe (II) EDTA-NO that Fe (II) EDTA complexing NO generates and Fe (III) EDTA that is produced by dioxygen oxidation part Fe (II) EDTA in the flue gas.
Wherein, the biofilm that three-dimensional electricity level is carried out Mixed Microbes is divided into some stages, and each stage may further comprise the steps:
(a) Mixed Microbes after will taming, nitrogen oxide complexed absorption product and basal medium mix, and make mixed solution;
(b) three-dimensional electricity level is inserted in the solution of step (a) preparation, reduction reaction is carried out in energising;
(c) after reaction is finished, reacted solution is discharged, reconfigure the mixed solution of Mixed Microbes, nitrogen oxide complexed absorption product and basal medium after the domestication, reduction reaction is carried out in energising, carries out the biofilm of next stage after the repeated several times;
Electrical current increases along with the propelling in biofilm stage, and the carbon source concentration in the basal medium reduces along with the propelling in biofilm stage.
Described carbonaceous material is graphite, anthracite or carbon fiber felt, and described conducting particles is agraphitic carbons such as active carbon, anthracite or carbon fiber, graphite granule, metal, vitreous carbon.Separate with barrier film, dividing plate or sleeve with holes between anode and cathode, the filled conductive particle is around negative electrode in the zone at negative electrode place.
Electrical current in the step (3) is 10～200mA, and reaction temperature is 30～60 ℃ in the step (3), and the pH value of mixed solution is 5～8 in the step (3).
The electron donor that is added is one or more in sulphite, disulfate, glucose, ethanol, the acetate; The carbon source that is added is one or more in glucose, ethanol, the acetate.The electron donor that adds provides energy source for the reduction activity of Mixed Microbes, the carbon source that adds provides the carbon element source for the growth of Mixed Microbes, glucose, ethanol, acetate have the difunctional nutrients of carbon source and energy function concurrently, be add electron donor and carbon source preferred, when electron donor and carbon source are same substance, can repeat to add.
Because the mixed culture of inoculating during the three-diemsnional electrode biofilm for denitrifying bacterium and iron-reducing bacterium, the biomembrane of formation can reduce Fe (II) EDTA-NO and Fe (III) EDTA simultaneously.
With Fe (II) EDTA is nitrogen oxide in the absorption liquid complexed absorption flue gas, generates Fe (II) EDTA-NO; Because contain part oxygen in the flue gas, part Fe (II) EDTA can be oxidized to Fe (III) EDTA in absorption process, thereby has Fe (II) EDTA-NO and Fe (III) EDTA in the nitrogen oxide complexed absorption product simultaneously simultaneously.Method of the present invention is Fe (II) EDTA-NO and Fe (III) EDTA in the reduction complexing absorption product simultaneously.After the mixed culture of inoculation denitrifying bacterium and iron-reducing bacterium carried out biofilm, the negative electrode particle filled composite of three-diemsnional electrode surface was with mixing mycoderm; After the three-dimensional physics electrifying electrodes, micro-electrolytic water, negative electrode discharges H
2, anode discharges CO
2, the denitrifying bacterium on the biomembrane utilizes H
2With a spot of electron donor that adds the NO of bonding is reduced to harmless N
2, the iron-reducing bacterium on the biomembrane utilizes H
2With a spot of electron donor that adds Fe (III) EDTA is reduced to Fe (II) EDTA, thereby realizes the regeneration of complexed absorption agent.
The electrode reaction formula is:
Positive C+2H
2O → CO
2+ 4H
++ 4e (e
0=0.207v);
Negative electrode 2H
2O+2e → H
2+ 2OH
-(e
0=0.000v)
The product CO of anode
2Be dissolved in water, and have part to be converted into H
2CO
3, CO
3 2-, HCO
3 -Deng, not only can be used as the carbon source of autotrophic microbe, also the pH value to system has cushioning effect.Is example with glucose as carbon source and electron donor, and its biochemical reaction formula is:
With hydrogen is that electron donor, DIC are carbon source, and its biochemical reaction formula is:
The present invention utilizes the clastic conductive material as particle filled composite, both can serve as the carrier of microbial adhesion, can form three-diemsnional electrode again and improve current efficiency.Owing to exist simultaneously in the three-diemsnional electrode biomembrane and utilize the CO that adds organic heterotrophic microorganism and utilize anode to produce
2Deng DIC is that the hydrogen that carbon source, micro-electrolytic water produce is the autotrophic microbe of electron donor, the wherein utilization of inorganic carbon source, raw material inputs such as organic matter have been saved, the hydrogen that utilizes the electrolysis generation on the other hand is as electron donor, accelerated the speed that electronics transmits in the reduction process, improve rate of reduction greatly, and hydroxide generation water, secondary pollution avoided.Method of the present invention is applicable to the regeneration of complexed absorption liquid in complexed absorption-biological reducing system, and simple to operate, financial cost is low, takes up an area of for a short time, and secondary pollution is little.
The specific embodiment
1, enrichment of microorganism and domestication
(1) microbial enrichment
Get sanitary sewage disposal factory denitrification pond mud, leave standstill 24h after, the elimination supernatant takes off layer mud 10mL and is inoculated in the 250mL nutrient solution that contains the 100mL basic culture solution, uses N
2Drive water seal behind the oxygen, place 40 ℃ constant temperature shaking table shaken cultivation, shaking speed 140r/min is with the Na NO of 1000mg/L
3 -Carry out enrichment culture as only nitrogen source, through about 14 days, treat NO in the nutrient solution
3 -Consumed and observed N in a large number
2After the generation, (5000r/min 15min), collects thalline, is mixed with bacterium liquid with the centrifugation of bacterium liquid.
(2) microbial acclimation
Get that above-mentioned bacterium liquid 10mL is inoculated in Fe (II) EDTA-NO respectively or Fe (III) EDTA concentration is in the 100mL basal medium of 2mmol/L, regulate pH value 6.5～7.0, put into the constant temperature shaking table and cultivate.Changed a nutrient solution in per six days, inoculation 10mL tames in the 100mL fresh medium, with 2mmol/L is gradient, progressively increase Fe (II) EDTA-NO or the concentration of Fe (III) EDTA in nutrient solution, make it finally reach 12mmol/L, tamed 30 days, and obtained the denitrifying bacterium liquid of reduction Fe (II) EDTA-NO and the iron-reducing bacterium liquid of reduction Fe (III) EDTA.
(3) Mixed Microbes domestication
Getting 5mL denitrifying bacterium liquid and 5mL iron-reducing bacterium liquid respectively, to be inoculated in Fe (II) EDTA-NO concentration be that 2mmol/L, Fe (III) EDTA concentration is in the 500mL basal medium of 10mmol/L, regulates pH value 6.5～7.0, puts into the constant temperature shaking table and cultivate.Reaching 90% of total iron with Fe (II) EDTA concentration is that nutrient solution is changed index, the inoculation 5mL last time bacterium liquid of enrichment continues Mixed culture in the 500mL fresh medium, with 2mmol/L is gradient, progressively increase the concentration of Fe (II) EDTA-NO in nutrient solution, make it finally reach 6mmol/L, total iron still keeps 12mmol/L, tames about 30 days, obtains the mixed culture of denitrifying bacterium and iron-reducing bacterium.
Basal medium (mg L
-1): carbon source (glucose) 2500, KH
2PO
4300, Na
2SO
370, MgCl
2100, NaHCO
35400, CaCl
22, CoCl
20.48, MnCl
24H
2O 1.98, CuSO
45H
2O 0.5, Na
2MoO
42H
2O 0.44, NiCl
26H
2O 0.38, H
3BO
40.028, ZnCl
20.2.The component of basal medium can be regulated, as long as can satisfy microbial growth.
2, prepare nitrogen oxide complexed absorption product
With equimolar soluble ferrite and Na
2EDTA2H
2O is mixed with certain density Fe (II) EDTA solution, uses 2mol L
-1NaOH regulate about pH value to 5.0, pour into again in the 250mL absorption bottle, feeding NO absorbs.When the NO exit concentration is consistent with inlet concentration, stop to absorb, obtain pH value and be 6.5～7.0 Fe (II) EDTA-NO saturated absorption liquid, drive oxygen sealing preservation.Wherein, soluble ferrite comprises FeSO
4, FeCl
2Perhaps Fe SO
4(NH
4)
2SO
4
3, the body plan of three-diemsnional electrode
The 3 D electrode reactor main body is a cylinder, and anode is made by graphite rod in the reaction vessel center, and four uniform on every side graphite rods are made negative electrode, and reactor is provided with the perforate cylinder of separating anode and cathode, fills activated carbon granule around the negative electrode graphite rod.Anode also can be made of other carbonaceous materials such as anthracite, carbon fiber felts, and negative electrode also can be made by metallic conductor except that can being made of other carbonaceous materials; Particle filled composite also can be made by other clastic conductive materials, as: other amorphous carbon such as anthracite, carbon fiber, metal, graphite granule or vitreous carbon; Separation between the anode and cathode also can be barrier film or dividing plate with holes.
4, the Mixed Microbes biofilm of three-diemsnional electrode
The Mixed Microbes of domestication in advance is seeded in the 3 D electrode reactor, adopts preface to criticize the method for operation, microorganism is carried out the domestication biofilm in some stages.The effective volume of reactor is 1L, and bath temperature is 50 ℃, and initial pH is 6.7～6.9, and the Mixed Microbes amount of each inoculation is 100mg L
-1By total concentration of iron 12mmol/L in the mixed solution of complexed absorption product and Fe (III) EDTA preparation, Fe (II) EDTA-NO concentration 4mmol/L.Biofilm progressively increase in each stage electrical current (0～30mA), reduce carbon source---the input amount (2500～1000mg/L) of glucose in the basal medium.In the domestication biofilm process, account for total iron ratio greater than 85% as the index of changing water stage by stage with Fe (II) EDTA behind the reactor operation 12h, next stage increase electrical current also reduces the culture medium concentration of glucose of mixed solution; Keep the culture medium concentration of glucose of electrical current and mixed solution constant when changing liquid in each stage, when Fe (II) EDTA accounts for total iron ratio greater than 85% as the index of changing water, each stage repeats to change liquid more than 3 times.Tame after 3 months, utilize environmental scanning electronic microscope technology (ESEM), observe the growing state of mixed culture on the negative electrode particle filled composite.Find particle filled composite surface microorganism quantity more for a long time when electron microscopy observation, just realized whole biofilm process.
5, reductive NO complexed absorption product
Embodiment 1
Will be by FeCl
24H
2O and Na
2H
2The water-soluble Fe that makes of EDTA (II) EDTA solution absorption of N O makes Fe (II) EDTA-NO solution.With FeCl
34H
2O and Na
2H
2Water-soluble Fe (III) the EDTA solution of making of EDTA.Basal medium concentrate, Fe (II) EDTA-NO solution and Fe (III) EDTA solution are made the 1L mixed solution, the pH value is adjusted to 6.5, (II) EDTA-NO of Fe in the solution and Fe (III) EDTA concentration are respectively 2mmol/L and 10mmol/L, basal medium other constituent concentration concentration except that concentration of glucose is 1500mg/L are constant, mixed solution poured in the three-diemsnional electrode biofilm reactor then; In temperature is under 50 ℃ of conditions, the reactor electrodes energising, and wherein electric current is 30mA, and reduction reaction is after 6 hours, and the Fe in the reactor (II) EDTA concentration is 9.5mmol/L.
Embodiment 2
Will be by FeSO
4(NH
4)
2SO
46H
2O and Na
2H
2The water-soluble Fe that makes of EDTA (II) EDTA solution absorption of N O makes Fe (II) EDTA-NO solution.With FeCl
34H
2O and Na
2H
2Water-soluble Fe (III) the EDTA solution of making of EDTA.Basal medium concentrate, Fe (II) EDTA-NO solution and Fe (III) EDTA solution are made the 1L mixed solution, the pH value is adjusted to 6.7, (II) EDTA-NO of Fe in the solution and Fe (III) EDTA concentration are respectively 4mmol/L and 8mmol/L, basal medium other constituent concentration concentration except that concentration of glucose is 1500mg/L are constant, mixed solution poured in the three-diemsnional electrode biofilm reactor then; In temperature is under 50 ℃ of conditions, the reactor electrodes energising, and wherein electric current is 50mA, and reduction reaction is after 9 hours, and the Fe in the reactor (II) EDTA concentration is 9.2mmol/L.
Embodiment 3
Will be by FeSO
4And Na
2H
2The water-soluble Fe that makes of EDTA (II) EDTA solution absorption of N O makes Fe (II) EDTA-NO solution.With FeCl
34H
2O and Na
2H
2Water-soluble Fe (III) the EDTA solution of making of EDTA.Basal medium concentrate, Fe (II) EDTA-NO solution and Fe (III) EDTA solution are made the 1L mixed solution, the pH value is adjusted to 6.8, (II) EDTA-NO of Fe in the solution and Fe (III) EDTA concentration are 6mmol/L, basal medium other constituent concentration concentration except that concentration of glucose is 1500mg/L are constant, mixed solution poured in the three-diemsnional electrode biofilm reactor then; In temperature is under 50 ℃ of conditions, the reactor electrodes energising, and wherein electric current is 30mA, and reduction reaction is after 12 hours, and the Fe in the reactor (II) EDTA concentration is 9.5mmol/L.
Embodiment 4
Will be by FeSO
4(NH
4)
2SO
46H
2O and Na
2H
2The water-soluble Fe that makes of EDTA (II) EDTA solution absorption of N O makes Fe (II) EDTA-NO solution.With FeCl
34H
2O and Na
2H
2Water-soluble Fe (III) the EDTA solution of making of EDTA.Basal medium concentrate, Fe (II) EDTA-NO solution and Fe (III) EDTA solution are made the 1L mixed solution, the pH value is adjusted to 6.8, (II) EDTA-NO of Fe in the solution and Fe (III) EDTA concentration are 6mmol/L, basal medium other constituent concentrations except that concentration of glucose is 2000mg/L are constant, mixed solution poured in the three-diemsnional electrode biofilm reactor then; In temperature is under 50 ℃ of conditions, the reactor electrodes energising, and wherein electric current is 50mA, and reduction reaction is after 6 hours, and the Fe in the reactor (II) EDTA concentration is 9.3mmol/L.
Embodiment 5
Will be by FeCl
24H
2O and Na
2H
2The water-soluble Fe that makes of EDTA (II) EDTA solution absorption of N O makes Fe (II) EDTA-NO solution.With FeCl
34H
2O and Na
2H
2Water-soluble Fe (III) the EDTA solution of making of EDTA.Basal medium concentrate, Fe (II) EDTA-NO solution and Fe (III) EDTA solution are made the 1L mixed solution, the pH value is adjusted to 6.8, (II) EDTA-NO of Fe in the solution and Fe (III) EDTA concentration are 6mmol/L, basal medium other constituent concentration concentration except that concentration of glucose is 1500mg/L are constant, mixed solution poured in the three-diemsnional electrode biofilm reactor then; In temperature is under 50 ℃ of conditions, the reactor electrodes energising, and wherein electric current is 100mA, and reduction reaction is after 9 hours, and the Fe in the reactor (II) EDTA concentration is 10.1mmol/L.
Claims (9)
1. be used for the method for denitrating flue gas regenerating nitrogen oxide complexed absorption liquid, may further comprise the steps:
(1) with the carbonaceous material be anode, metallic conductor or carbonaceous material are negative electrode, and the filled conductive particle is made three-diemsnional electrode around negative electrode;
(2), make with three-dimensional electric grade that mixes mycoderm with three-dimensional electric grade of biofilm of carrying out Mixed Microbes;
Described Mixed Microbes is the mixed culture of denitrifying bacterium and iron-reducing bacterium;
(3) add electron donor, carbon source and basal medium and in nitrogen oxide complexed absorption product, make mixed solution, will insert in the mixed solution and energising with the three-diemsnional electrode that mixes mycoderm then, carry out reduction reaction.
2. the method for claim 1 is characterized in that: the biofilm that three-dimensional electricity level is carried out Mixed Microbes is divided into some stages, and each stage may further comprise the steps:
(a) Mixed Microbes after will taming, nitrogen oxide complexed absorption product and basal medium mix, and make mixed solution;
(b) three-dimensional electricity level is inserted in the solution of step (a) preparation, reduction reaction is carried out in energising;
(c) after reaction is finished, reacted solution is discharged, reconfigure the mixed solution of Mixed Microbes, nitrogen oxide complexed absorption product and basal medium after the domestication, reduction reaction is carried out in energising, carries out the biofilm of next stage after the repeated several times;
Electrical current increases along with the propelling in biofilm stage, and the carbon source concentration in the basal medium reduces along with the propelling in biofilm stage.
3. renovation process as claimed in claim 1 is characterized in that: described carbonaceous material is graphite, anthracite or carbon fiber felt.
4. renovation process as claimed in claim 1 is characterized in that: described conducting particles is agraphitic carbon, carbon fiber, graphite granule, metal or vitreous carbon.
5. renovation process as claimed in claim 1 is characterized in that: the electrical current in the step (3) is 10～200mA.
6. renovation process as claimed in claim 1 is characterized in that: reaction temperature is 30～60 ℃ in the step (3).
7. renovation process as claimed in claim 1 is characterized in that: the pH value of mixed solution is 5～8 in the step (3).
8. renovation process as claimed in claim 1 is characterized in that: the electron donor that is added is one or more in sulphite, disulfate, glucose, ethanol, the acetate; The carbon source that is added is one or more in glucose, ethanol, the acetate.
9. renovation process as claimed in claim 1 is characterized in that: the concentration of electron donor in mixed solution is 3～15mmol/L, and the concentration of carbon source in mixed solution is 3～15mmol/L.
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| CN102553434A (en) * | 2012-03-06 | 2012-07-11 | 浙江大学 | Device and method for purifying nitrogen oxides in flue gas by utilizing electrode biological membrane |
| CN102676430A (en) * | 2012-05-10 | 2012-09-19 | 大连理工大学 | Paracoccus denitrifican with denitrification and iron reduction functions and culturing method and application thereof |
| CN102716654A (en) * | 2012-06-01 | 2012-10-10 | 上海交通大学 | Method and device for flue gas denitration by spray absorption and electrochemical reduction |
| CN103123976A (en) * | 2013-02-27 | 2013-05-29 | 上海大学 | Fe(II)EDTA regeneration method based on microbial fuel cell |
| CN105032152A (en) * | 2015-07-24 | 2015-11-11 | 大连理工大学 | Chemical absorption and microbial fuel cell combined synchronous flue gas desulfurization and denitration technology |
| CN106630117A (en) * | 2016-12-16 | 2017-05-10 | 北京泷涛环境科技有限公司 | Three-dimensional electrode-biological membrane combined method for degrading organic pollutants and performing denitrification |
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| CN102553434A (en) * | 2012-03-06 | 2012-07-11 | 浙江大学 | Device and method for purifying nitrogen oxides in flue gas by utilizing electrode biological membrane |
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| CN102716654A (en) * | 2012-06-01 | 2012-10-10 | 上海交通大学 | Method and device for flue gas denitration by spray absorption and electrochemical reduction |
| CN103123976A (en) * | 2013-02-27 | 2013-05-29 | 上海大学 | Fe(II)EDTA regeneration method based on microbial fuel cell |
| CN103123976B (en) * | 2013-02-27 | 2016-01-13 | 上海大学 | Based on Fe (II) the EDTA renovation process of microbiological fuel cell |
| CN105032152A (en) * | 2015-07-24 | 2015-11-11 | 大连理工大学 | Chemical absorption and microbial fuel cell combined synchronous flue gas desulfurization and denitration technology |
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